U.S. patent application number 14/226907 was filed with the patent office on 2014-10-02 for urethane based extenders for surface effect compositions.
This patent application is currently assigned to E I DU PONT DE NEMOURS AND COMPANY. The applicant listed for this patent is E I DU PONT DE NEMOURS AND COMPANY. Invention is credited to Gerald Oronde BROWN, Flemming Vang SPARSOE, John Christopher SWOREN, Mario VINCENZINI.
Application Number | 20140296123 14/226907 |
Document ID | / |
Family ID | 50640014 |
Filed Date | 2014-10-02 |
United States Patent
Application |
20140296123 |
Kind Code |
A1 |
SWOREN; John Christopher ;
et al. |
October 2, 2014 |
URETHANE BASED EXTENDERS FOR SURFACE EFFECT COMPOSITIONS
Abstract
A method of treating a substrate comprising contacting the
substrate with a composition comprising i) an agent which provides
a surface effect and ii) a polymer extender composition comprising
a urethane based compound, a composition for treating a substrate,
and treated substrates thereof.
Inventors: |
SWOREN; John Christopher;
(Chadds Ford, PA) ; BROWN; Gerald Oronde;
(Wilmington, DE) ; VINCENZINI; Mario;
(Coatesville, PA) ; SPARSOE; Flemming Vang;
(Skanderborg, DK) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
E I DU PONT DE NEMOURS AND COMPANY |
Wilmington |
DE |
US |
|
|
Assignee: |
E I DU PONT DE NEMOURS AND
COMPANY
Wilmington
DE
|
Family ID: |
50640014 |
Appl. No.: |
14/226907 |
Filed: |
March 27, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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61806458 |
Mar 29, 2013 |
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Current U.S.
Class: |
510/299 ;
510/276; 510/327; 524/507; 525/123 |
Current CPC
Class: |
D06M 2200/10 20130101;
D06M 2200/35 20130101; D06M 2200/11 20130101; D06M 15/572 20130101;
C08G 18/36 20130101; D06M 2200/12 20130101; D06M 15/277 20130101;
D06M 15/263 20130101; D06M 15/568 20130101; D06M 15/643 20130101;
C08L 75/06 20130101; C11D 3/001 20130101; D06M 15/53 20130101; D06M
15/227 20130101; D06M 2200/20 20130101; D06M 15/267 20130101; C11D
3/0036 20130101; D06M 15/564 20130101; C11D 3/0005 20130101; D06M
2200/01 20130101; D06M 2200/45 20130101; D06M 2200/50 20130101;
C08L 75/08 20130101; D21H 19/24 20130101; C08G 18/6279 20130101;
C11D 3/3726 20130101; D06M 15/576 20130101; C08G 18/7831 20130101;
C08G 18/792 20130101; C08G 18/80 20130101; C08L 33/10 20130101;
D06M 15/295 20130101 |
Class at
Publication: |
510/299 ;
525/123; 524/507; 510/327; 510/276 |
International
Class: |
C08L 75/08 20060101
C08L075/08; C08L 75/06 20060101 C08L075/06; C11D 3/00 20060101
C11D003/00; C08L 33/10 20060101 C08L033/10 |
Claims
1. A method of treating a substrate comprising contacting the
substrate with a composition comprising i) an agent which provides
a surface effect and ii) a polymer extender composition comprising
a compound prepared by: (i) reacting (a) at least one isocyanate
group-containing compound selected from isocyanate, diisocyanate,
polyisocyanate, or mixture thereof, and (b) at least one
isocyanate-reactive compound selected from formula (Ia), (Ib), or
(Ic): ##STR00005## wherein each R is independently a --H;
--R.sup.1; --C(O)R.sup.1;
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mR.sup.2; or
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mC(O)R.sup.1;
each n is independently 0 to 20; each m is independently 0 to 20;
m+n is greater than 0; each R.sup.1 is independently a linear or
branched alkyl group having 5 to 29 carbons optionally comprising
at least 1 unsaturated bond; each R.sup.2 is independently --H, or
a linear or branched alkyl group having 6 to 30 carbons optionally
comprising at least 1 unsaturated bond; or a mixtures thereof,
provided that when the compound is of Formula (Ia) then at least
one of R or R.sup.2 is --H; each R.sup.3 is independently a --H;
--R.sup.1; --C(O)R.sup.1;
--(CH.sub.2CH.sub.2O).sub.n'(CH(CH.sub.3)CH.sub.2O).sub.m'R.sup.2;
or
--(CH.sub.2CH.sub.2O).sub.n'(CH(CH.sub.3)CH.sub.2O).sub.m'C(O)R.sup.1;
each R.sup.4 is independently --H, a linear or branched alkyl group
having 6 to 30 carbons optionally comprising at least 1 unsaturated
bond, or combinations thereof;
--(CH.sub.2CH.sub.2O).sub.n'(CH(CH.sub.3)CH.sub.2O).sub.m'R.sup.2;
or
--(CH.sub.2CH.sub.2O).sub.n'(CH(CH.sub.3)CH.sub.2O).sub.m'C(O)R.sup.1;
each n' is independently 0 to 20; each m' is independently 0 to 20;
m'+n' is greater than 0; provided when the compound is Formula
(Ib), then at least one R.sup.2, R.sup.3 or R.sup.4 is a --H; and
each R.sup.19 is --H, --C(O)R.sup.1, or
--CH.sub.2C[CH.sub.2OR].sub.3, provided when the compound is
Formula (Ic), then at least one R.sup.19 or R is --H.
2. A method according to claim 1, wherein the compounds of formulas
(Ia), (Ib), and (Ic) are at least 50% bio-based derived.
3. A method according to claim 1, wherein the compounds of formulas
(Ia), (Ib), and (Ic) are 100% bio-based derived.
4. A method according to claim 1, wherein the diioscyanate or
polyisocyanate is selected from the group consisting of
hexamethylene diisocyanate homopolymer,
3-isocyanatomethyl-3,4,4-trimethylcyclohexyl isocyanate,
bis-(4-isocyanatocylohexyl)methane and diisocyanate trimers of
formulas (IIa), (IIIb), (IIc) and (IId): ##STR00006##
6. A method according to claim 1, wherein step (i) further
comprises reacting (c) at least one second compound selected from
water, at least one organic compound of Formula (IIIa) R.sup.5--X
(IIIa), at least one organic compound of Formula (IIIb)
R.sup.15--(OCH.sub.2CH(OR.sup.16)CH.sub.2).sub.z--OR.sup.17 (IIIb),
or mixtures thereof; wherein R.sup.5 is selected from a --C.sub.1
to C.sub.30 linear or branched alkyl optionally comprising at least
one unsaturated group, a hydroxy-functional C.sub.1 to C.sub.30
linear or branched alkyl, a hydroxy-functional linear or branched
C.sub.1 to C.sub.30 polyether, a hydroxy-functional linear or
branched polyester, a hydroxy- or amine-functional linear or
branched organosiloxane, a thiol-functional C.sub.1 to C.sub.30
linear or branched alkyl, an amine-functional C.sub.1 to C.sub.30
linear or branched alkyl, ##STR00007## wherein R.sup.7, R.sup.8,
and R.sup.9 are each independently, --H, --C.sub.1 to C.sub.6
alkyl, or combinations thereof; R.sup.10 is a divalent alkyl group
of 1 to 20 carbons; X is an isocyanate-reactive group selected from
--OH, --C(O)OH, --SH, --NH(R.sup.12),
--O--(CH.sub.2CH.sub.2O).sub.s(CH(CH.sub.3)CH.sub.2O).sub.t--H or
--[C(O)]--O--(CH.sub.2CH.sub.2O).sub.s(CH(CH.sub.3)CH.sub.2O).sub.t--H;
R.sup.12 is --H or a monovalent C1 to C6 alkyl group; R.sup.15,
R.sup.16, and R.sup.17 are each independently a --H; --R.sup.18;
--C(O)R.sup.18 provided that at least one R.sup.15, R.sup.16, or
R.sup.17 is a --H; R.sup.18 is independently a linear or branched
alkyl group having 5 to 29 carbons optionally comprising at least 1
unsaturated bond; z is 1 to 15; Y is --Cl; s is an integer of 0 to
50; t is an integer of 0 to 50; s+t is greater than 0.
7. A method according to claim 6, wherein the second compound (c)
is of Formula (IIIa), and X is
--O--(CH.sub.2CH.sub.2O).sub.s(CH(CH.sub.3)CH.sub.2O).sub.t--H; or
--[C(O)]--O--(CH.sub.2CH.sub.2O).sub.s(CH(CH.sub.3)CH.sub.2O).sub.t--H.
8. A method according to claim 6, wherein the second compound (c)
is of Formula (IIIa), X is an isocyanate-reactive functional group
selected from --OH, --C(O)OH, --SH, --NH(R.sup.12); and R.sup.5 is
selected from a --C.sub.1 to C.sub.30 linear or branched alkyl
optionally comprising at least one unsaturated group, a
hydroxy-functional C.sub.1 to C.sub.30 linear or branched alkyl, a
hydroxy-functional linear or branched C.sub.1 to C.sub.30
polyether, a hydroxy-functional linear or branched polyester, a
hydroxy-functional linear or branched organosiloxane, a
thiol-functional C.sub.1 to C.sub.30 linear or branched alkyl, an
amine-functional C.sub.1 to C.sub.30 linear or branched alkyl.
9. A method according to claim 6, wherein the second compound (c)
is of Formula (IIIb).
10. A method according to claim 6, wherein (b) is at least one
compound selected from formula (Ia): ##STR00008## wherein R is
independently a --H; --R.sup.1; or --C(O)R.sup.1.
11. A method according to claim 6, wherein (b) is at least one
compound selected from formula (Ia): ##STR00009## wherein R is
independently a --H;
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mR.sup.2; or
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mC(O)R.sup.1.
12. A method according to claim 6, wherein (b) is at least one
compound selected from formula (Ib): ##STR00010##
13. A method according to claim 6 wherein (b) is at least one
compound selected from formula (Ic): ##STR00011##
14. The method of claim 1 wherein the surface effect is no iron,
easy to iron, shrinkage control, wrinkle free, permanent press,
moisture control, softness, strength, anti-slip, anti-static,
anti-snag, anti-pill, stain repellency, stain release, soil
repellency, soil release, water repellency, oil repellency, odor
control, antimicrobial, sun protection, and similar effects.
15. The method of claim 14 wherein the agent is selected from the
group consisting of non-fluorinated cationic acrylic polymers,
non-fluorinated anionic acrylic polymers, non-fluorinated nonionic
acrylic polymers, partially fluorinated urethanes, cationic
partially fluorinated acrylic polymers or copolymers, nonionic
partially fluorinated acrylic polymers or copolymers, partially
fluorinated acrylamide polymers or copolymers, silicones, and
parafins.
16. The method of claim 14 wherein the ratio of the extender
composition to the agent is from about 1:10 to about 10:1.
17. The method of claim 1 wherein the composition further comprises
a blocked isocyanate.
18. The method of claim 1 wherein the composition further comprises
an additive selected from the group consisting of a surfactant,
emulsifier, pH adjuster, crosslinker, wetting agent, and
softener.
19. The method of claim 1 wherein the substrate is a fiber,
textile, fabric, fabric blend, paper, nonwoven, leather or
combination thereof.
20. A substrate treated by the method of claim 1.
21. A composition for treating a substrate comprising i) an agent
which provides a surface effect and ii) a polymer extender
composition comprising a compound prepared by: (i) reacting (a) at
least one isocyanate group-containing compound selected from
isocyanate, diisocyanate, polyisocyanate, or mixture thereof, and
(b) at least one isocyanate-reactive compound selected from formula
(Ia), (Ib), or (Ic): ##STR00012## wherein each R is independently a
--H; --R.sup.1; --C(O)R.sup.1;
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mR.sup.2; or
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mC(O)R.sup.1;
each n is independently 0 to 20; each m is independently 0 to 20;
m+n is greater than 0; each R.sup.1 is independently a linear or
branched alkyl group having 5 to 29 carbons optionally comprising
at least 1 unsaturated bond; each R.sup.2 is independently --H, or
a linear or branched alkyl group having 6 to 30 carbons optionally
comprising at least 1 unsaturated bond; or a mixtures thereof,
provided that when the compound is of Formula (Ia) then at least
one of R or R.sup.2 is --H; each R.sup.3 is independently a --H;
--R.sup.1; --C(O)R.sup.1;
--(CH.sub.2CH.sub.2O).sub.n'(CH(CH.sub.3)CH.sub.2O).sub.m'R.sup.2;
or
--(CH.sub.2CH.sub.2O).sub.n'(CH(CH.sub.3)CH.sub.2O).sub.m'C(O)R.sup.1;
each R.sup.4 is independently --H, a linear or branched alkyl group
having 6 to 30 carbons optionally comprising at least 1 unsaturated
bond, or combinations thereof;
--(CH.sub.2CH.sub.2O).sub.n'(CH(CH.sub.3)CH.sub.2O).sub.m'R.sup.2;
or
--(CH.sub.2CH.sub.2O).sub.n'(CH(CH.sub.3)CH.sub.2O).sub.m'C(O)R.sup.1;
each n' is independently 0 to 20; each m' is independently 0 to 20;
m'+n' is greater than 0; provided when the compound is Formula
(Ib), then at least one R.sup.2, R.sup.3 or R.sup.4 is a --H; and
each R.sup.19 is --H, --C(O)R.sup.1, or
--CH.sub.2C[CH.sub.2OR].sub.3, provided when the compound is
Formula (Ic), then at least one R.sup.19 or R is --H.
22. The composition of claim 21, wherein the diioscyanate or
polyisocyanate is selected from the group consisting of
hexamethylene diisocyanate homopolymer,
3-isocyanatomethyl-3,4,4-trimethylcyclohexyl isocyanate,
bis-(4-isocyanatocylohexyl)methane and diisocyanate trimers of
formulas (IIa), (IIb), (IIc) and (IId): ##STR00013##
23. The composition of claim 21, wherein step (i) further comprises
reacting (c) at least one second compound selected from water, at
least one organic compound of Formula (IIIa) R.sup.5--X (IIIa), at
least one organic compound of Formula (IIIb)
R.sup.15--(OCH.sub.2CH(OR.sup.16)CH.sub.2).sub.z--OR.sup.17 (IIIb),
or mixtures thereof; wherein R.sup.5 is selected from a --C.sub.1
to C.sub.30 linear or branched alkyl optionally comprising at least
one unsaturated group, a hydroxy-functional C.sub.1 to C.sub.30
linear or branched alkyl, a hydroxy-functional linear or branched
C.sub.1 to C.sub.30 polyether, a hydroxy-functional linear or
branched polyester, a hydroxy- or amine-functional linear or
branched organosiloxane, a thiol-functional C.sub.1 to C.sub.30
linear or branched alkyl, an amine-functional C.sub.1 to C.sub.30
linear or branched alkyl, ##STR00014## wherein R.sup.7, R.sup.8,
and R.sup.9 are each independently, --H, --C.sub.1 to C.sub.6
alkyl, or combinations thereof; R.sup.10 is a divalent alkyl group
of 1 to 20 carbons; X is an isocyanate-reactive group selected from
--OH, --C(O)OH, --SH, --NH(R.sup.12),
--O--(CH.sub.2CH.sub.2O).sub.s(CH(CH.sub.3)CH.sub.2O).sub.t--H or
--[C(O)]--O--(CH.sub.2CH.sub.2O).sub.s(CH(CH.sub.3)CH.sub.2O).sub.t--H;
R.sup.12 is --H or a monovalent C1 to C6 alkyl group; R.sup.15,
R.sup.16, and R.sup.17 are each independently a --H; --R.sup.18;
--C(O)R.sup.18 provided that at least one R.sup.15, R.sup.16, or
R.sup.17 is a --H; R.sup.18 is independently a linear or branched
alkyl group having 5 to 29 carbons optionally comprising at least 1
unsaturated bond; z is 1 to 15; Y is --Cl; s is an integer of 0 to
50; t is an integer of 0 to 50; s+t is greater than 0.
Description
FIELD OF THE INVENTION
[0001] Hydrocarbon polymers are employed as extenders to improve
the performance of treating agents which provide surface effects to
treated substrates.
BACKGROUND OF THE INVENTION
[0002] Various compositions are known to be useful as treating
agents to provide surface effects to substrates. Surface effects
include repellency to moisture, soil and stain resistance, and
other effects which are particularly useful for fibrous substrates
such as fibers, fabrics, textiles, carpets, paper, leather and
other such substrates. Many such treating agents are partially
fluorinated polymers or copolymers.
[0003] Fluorinated polymer compositions having utility as fibrous
substrate treating agents generally contain pendant perfluoroalkyl
groups of three or more carbon atoms, which provide oil- and
water-repellency when the compositions are applied to fibrous
substrate surfaces. The perfluoroalkyl groups are generally
attached by various connecting groups to polymerizable groups not
containing fluorine. The resulting monomer is then generally
copolymerized with other monomers which confer additional favorable
properties to the substrates. Various specialized monomers may be
incorporated to impart improved cross-linking, latex stability and
substantivity. Since each ingredient may impart some potentially
undesirable properties in addition to its desirable ones, the
specific combination is directed to the desired use. These polymers
are generally marketed as aqueous emulsions for easy application to
the fibrous substrates.
[0004] Various attempts have been made to increase the oil- and
water-repellency imparted to the substrate and its durability while
reducing the amount of fluorinated polymer required, i.e., boost
the efficiency or performance of the treating agent. One method is
to incorporate blocked isocyanates or melamine resins. However,
only limited amounts can be used because these ingredients tend to
adversely affect the handle (the feel) of the fibrous substrate.
Another approach employs use of various extender polymers. These
are typically hydrocarbon polymers in aqueous emulsions, which are
blended with the fluorinated polymer emulsion before application to
the substrate.
[0005] U.S. Pat. No. 7,344,758 discloses an emulsion suitable for
imparting oil and/or water-repellency to substrates, containing a
fluorinated acrylate copolymer.
BRIEF SUMMARY OF THE INVENTION
[0006] There is a need for polymer compositions which significantly
improve the performance of surface effect agents. In particular,
there is a need for compositions which improve the durability of
surface effects for substrates while reducing the amount of
fluorinated polymer required. The present invention provides such a
composition.
[0007] The present invention comprises a method of treating a
substrate comprising contacting the substrate with a composition
comprising i) an agent which provides a surface effect and ii) a
polymer extender composition comprising a compound prepared by: (i)
reacting (a) at least one isocyanate group-containing compound
selected from isocyanate, diisocyanate, polyisocyanate, or mixture
thereof, and (b) at least one isocyanate-reactive compound selected
from formula (Ia), (Ib), or (Ic):
##STR00001##
[0008] wherein each R is independently a --H; --R.sup.1;
--C(O)R.sup.1;
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mR.sup.2; or
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mC(O)R.sup.1;
[0009] each n is independently 0 to 20;
[0010] each m is independently 0 to 20;
[0011] m+n is greater than 0;
[0012] each R.sup.1 is independently a linear or branched alkyl
group having 5 to 29 carbons optionally comprising at least 1
unsaturated bond;
[0013] each R.sup.2 is independently --H, or a linear or branched
alkyl group having 6 to 30 carbons optionally comprising at least 1
unsaturated bond;
[0014] or a mixtures thereof,
[0015] provided that when the compound is of Formula (Ia) then at
least one of R or R.sup.2 is --H;
[0016] each R.sup.3 is independently a --H; --R.sup.1;
--C(O)R.sup.1;
--(CH.sub.2CH.sub.2O).sub.n'(CH(CH.sub.3)CH.sub.2O).sub.m'R.sup.2;
or
--(CH.sub.2CH.sub.2O).sub.n'(CH((CH.sub.3)CH.sub.2).sub.m'C(O)R.sup.1;
[0017] each R.sup.4 is independently --H, a linear or branched
alkyl group having 6 to 30 carbons optionally comprising at least 1
unsaturated bond, or combinations thereof;
--(CH.sub.2CH.sub.2O).sub.n'(CH(CH.sub.3)CH.sub.2O).sub.m'R.sup.2;
or
--(CH.sub.2CH.sub.2O).sub.n'(CH(CH.sub.3)CH.sub.2O).sub.m'C(O)R.sup.1;
[0018] each n' is independently 0 to 20;
[0019] each m' is independently 0 to 20;
[0020] m'+n' is greater than 0;
[0021] provided when the compound is Formula (Ib), then at least
one R.sup.2, R.sup.3 or R.sup.4 is a --H; and
[0022] each R.sup.19 is --H, --C(O)R.sup.1, or
--CH.sub.2C[CH.sub.2OR].sub.3,
[0023] provided when the compound is Formula (Ic), then at least
one R.sup.19 or R is --H.
[0024] The present invention further comprises a substrate treated
with a composition comprising a treating agent which when applied
to a substrate provides a surface effect and the above-described
extender composition.
[0025] The present invention further comprises a composition for
treating a substrate comprising i) an agent which provides a
surface effect and ii) a polymer extender composition comprising a
compound prepared by: (i) reacting (a) at least one isocyanate
group-containing compound selected from isocyanate, diisocyanate,
polyisocyanate, or mixture thereof, and (b) at least one
isocyanate-reactive compound selected from formula (Ia), (Ib), or
(Ic).
DETAILED DESCRIPTION OF THE INVENTION
[0026] Trademarks are indicated herein by capitalization.
[0027] The present invention comprises a method of treating a
substrate comprising contacting said substrate with a composition
comprising a treating agent, which when applied to a substrate
provides a surface effect, and an extender composition. In
particular, the extender composition is a non-fluorinated urethane
useful for improving the performance of fluorinated polymers in
imparting durable repellent properties to fibrous substrates. The
fibrous substrates include fibers, textiles, paper, nonwovens,
leather, carpets, fabrics, fabric blends or a combination thereof.
By "fabrics" is meant natural or synthetic fabrics, or blends
thereof, composed of fibers such as cotton, rayon, silk, wool,
polyester, polypropylene, polyolefins, nylon, and aramids such as
"NOMEX" and "KEVLAR." By "fabric blends" is meant fabric made of
two or more types of fibers. Typically these blends are a
combination of at least one natural fiber and at least one
synthetic fiber, but also can be a blend of two or more natural
fibers or of two or more synthetic fibers.
[0028] Superior durable surface properties, along with desirable
properties of low yellowing and good durability, are imparted to
fibrous substrates by the addition of the inventive extender
composition to surface treating agents before application to
fibrous substrates. These combined blends are applied to the
fibrous substrates in the form of a dispersion in water or other
solvent either before, after or during the application of other
treatment chemicals.
[0029] When so applied, the extender composition useful in this
invention, in combination with a treating agent, has been found in
particular to improve the durability of surface properties,
especially oil- and water-repellency, in fibrous substrates after
laundering by as much as 50%. The durability of the repellency is
improved compared to other known extender compositions. Further,
use of the extender composition of the present invention increases
fluorine efficiency of fluorinated treating agents by permitting
use of lower levels of the fluorinated polymer.
[0030] The aqueous dispersion blends produced by mixing the
extender composition dispersion with a treating agent dispersion
are applied to surfaces of fibrous substrates by known methods to
impart oil-, soil- and water-repellency and other surface effects.
A distinguishing feature of use of the treating agent-extender
compositions of the present invention is high durability of the
surface finish on the substrate.
[0031] The extender composition useful in the present invention
comprises a compound prepared by:
[0032] (i) reacting (a) at least one isocyanate group-containing
compound selected from isocyanate, diisocyanate, polyisocyanate, or
mixture thereof, and (b) at least one isocyanate-reactive compound
selected from formula (Ia), (Ib), or (Ic):
##STR00002##
[0033] wherein each R is independently a --H; --R.sup.1;
--C(O)R.sup.1;
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mR.sup.2; or
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mC(O)R.sup.1;
[0034] each n is independently 0 to 20;
[0035] each m is independently 0 to 20;
[0036] m+n is greater than 0;
[0037] each R.sup.1 is independently a linear or branched alkyl
group having 5 to 29 carbons optionally comprising at least 1
unsaturated bond;
[0038] each R.sup.2 is independently --H, or a linear or branched
alkyl group having 6 to 30 carbons optionally comprising at least 1
unsaturated bond;
[0039] or a mixtures thereof,
[0040] provided that when the compound is of Formula (Ia) then at
least one of R or R.sup.2 is --H;
[0041] each R.sup.3 is independently a --H; --R.sup.1;
--C(O)R.sup.1;
--(CH.sub.2CH.sub.2O).sub.n'(CH(CH.sub.3)CH.sub.2O).sub.mR.sup.2;
or
--(CH.sub.2CH.sub.2O).sub.n'(CH(CH.sub.3)CH.sub.2O).sub.m'C(O)R.sup.1;
[0042] each R.sup.4 is independently --H, a linear or branched
alkyl group having 6 to 30 carbons optionally comprising at least 1
unsaturated bond, or combinations thereof;
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.m'R.sup.2;
or
--(CH.sub.2CH.sub.2O).sub.n'(CH(CH.sub.3)CH.sub.2O).sub.mC(O)R.sup.1;
[0043] each n' is independently 0 to 20;
[0044] each m' is independently 0 to 20;
[0045] m'+n' is greater than 0;
[0046] provided when the compound is Formula (Ib), then at least
one R.sup.2, R.sup.3 or R.sup.4 is a --H; and
[0047] each R.sup.19 is --H, --C(O)R.sup.1, or
--CH.sub.2C[CH.sub.2OR].sub.3,
[0048] provided when the compound is Formula (Ic), then at least
one R.sup.19 or R is --H.
[0049] For compounds of Formula (Ia), (Ib), or (Ic), the
--(CH.sub.2CH.sub.2O)-- represents oxyethylene groups (EO) and
--(CH(CH.sub.3)CH.sub.2O)-- represents oxypropylene groups (PO).
These compounds can contain only EO groups, only PO groups, or
mixtures thereof. These compounds can also be present as a
tri-block copolymer designated PEG-PPG-PEG (polyethylene
glycol-polypropylene glycol-polyethylene glycol), for example.
[0050] In one embodiment, a polymer extender compound is prepared
by: (i) reacting (a) at least one isocyanate group-containing
isocyanate, diisocyanate, polyisocyanate, or mixture thereof, and
compounds of Formula (Ia). Compounds of Formula (Ia) where at least
one of R is --H and at least one R is selected from --C(O)R.sup.1
are commonly known as alkyl sorbitans. These sorbitans can be
mono-substituted, di-substituted, or tri-substituted with
--C(O)R.sup.1. It is known that commercially available sorbitans,
such as SPAN, contain a mixture of the various sorbitans ranging
from where each R is H (un-substituted), and sorbitans where each R
is --C(O)R.sup.1 (fully substituted); wherein R.sup.1 is a linear
or branched alkyl group having 5 to 29 carbons; and mixtures of
various substitutions thereof. The commercially available sorbitans
may also include amounts of sorbitol, isosorbide, or other
intermediates or byproducts.
[0051] In one preferred embodiment, at least one R is
--C(O)R.sup.1, and R.sup.1 is a linear branched alkyl group having
5 to 29 carbons, more preferably 7 to 21 carbons, and most
preferably 11 to 21 carbons. Preferred compounds include mono-,
di-, and tri-substituted sorbitans derived from caprylic acid,
capric acid, lauric acid, mysteric acid, palmitic acid, stearic
acid, arachidic acid, behenic acid, lignoceric acid, and mixtures
thereof. Particularly preferred compounds include mono-, di-, and
tri-substituted sorbitan stearates or sorbitan behenins.
[0052] Optionally, R.sup.1 is a linear or branched alkyl group
having 5 to 29 carbons comprising at least 1 unsaturated bond.
Examples of compounds of Formula (Ia) wherein at least one R is
selected from --C(O)R.sup.1; and R.sup.1 contains least 1
unsaturated bond, include, but are not limited to, sorbitan
trioleate (i.e., wherein R.sup.1 is
--C.sub.7H.sub.14CH.dbd.CHC.sub.8H.sub.17). Other examples but are
not limited to include mono-, di-, and tri-substituted sorbitans
derived from palmitoleic acid, lineolic acid, arachidonic acid, and
erucic acid.
[0053] In one embodiment, a compound of Formula (Ia) is employed,
wherein at least one R is independently
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mR.sup.2 or
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mC(O)R.sup.1.
Compounds of Formula (Ia), wherein at least one R is
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mR.sup.2 or
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mC(O)R.sup.1,
wherein each m is independently 0 to 20, each n is independently 0
to 20, and n+m is greater than 0 are known as polysorbates and are
commercially available under the tradename TWEEN. These
polysorbates can be mono-substituted, di-substituted, or
tri-substituted with alkyl groups R.sup.1 or R.sup.2. It is known
that commercially available polysorbates, contain a mixture of the
various polysorbates ranging from where each R.sup.2 is H
(unsubstituted), and polysorbates where each R.sup.1 is a linear or
branched alkyl group having 5 to 29 carbons (fully substituted);
and mixtures of various substitutions thereof. Examples of
compounds of Formula (Ia) include polysorbates such as polysorbate
tristearate, and polysorbate monostearate. Examples of compounds of
Formula (Ia) wherein m+n is greater than 0, and wherein R.sup.1
comprises at least 1 unsaturated bond, but not limited to,
polysorbate trioleate (wherein R.sup.1 is
C.sub.7H.sub.14CH.dbd.CHC.sub.8H.sub.17) and are sold commercially
under the name Polysorbate 80. Reagents may include mixtures of
compounds having various values for R, R.sup.1, and R.sup.2, and
may also include mixtures of compounds where R.sup.1 comprises at
least one unsaturated bond with compounds where R.sup.1 is fully
saturated.
[0054] Compounds of Formula (Ib) are known as alkyl citrates. These
citrates can be present as a mono-substituted, di-substituted, or
tri-substituted with alkyl groups. It is known that commercially
available citrates contain a mixture of the various citrates as
well as citric acids from where R.sup.3 and each R.sup.4 is --H,
ranging to citrates where each R.sup.4 is a linear or branched
alkyl group having 6 to 30 carbons optionally comprising at least 1
unsaturated bond; and mixtures of various substitutions thereof.
Mixtures of citrates having various values for R.sup.1, R.sup.2,
R.sup.3, and R.sup.4 may be used, and may also include mixtures of
compounds where R.sup.1 comprises at least one unsaturated bond
with compounds where R.sup.1 is fully saturated. Alkyl citrates are
also commercially available wherein m'+n' is greater than 0,
R.sup.4 is
--(CH.sub.2CH.sub.2O).sub.n'(CH(CH.sub.3)CH.sub.2O).sub.m'R.sup.2;
or
--(CH.sub.2CH.sub.2O).sub.n'(CH(CH.sub.3)CH.sub.2O).sub.m'C(O)R.sup.1
and are present in the various substitutions from wherein R.sup.3
and each R.sup.2 is H to wherein each R.sup.1 and/or R.sup.2 is a
linear or branched alkyl group having 5 to 30 carbons optionally
comprising at least 1 unsaturated bond. Examples of compounds of
Formula (Ib) include, but are not limited to, trialkyl
citrates.
[0055] Compounds of Formula (Ic) are known as pentaerythriol
esters. These pentaerythriol esters can be present as a
mono-substituted, di-substituted, or tri-substituted with alkyl
groups. Preferred compounds of Formula (Ic) are dipentaerythriol
esters, where R.sup.19 is --CH.sub.2C[CH.sub.2OR].sub.3. It is
known that commercially available pentaerythriol esters contain a
mixture of the various pentaerythriol esters where R.sup.19 and
each R is --H, ranging to pentaerythriol esters where each R is
--C(O)R.sup.1, and R.sup.1 is a linear or branched alkyl group
having 5 to 29 carbons optionally comprising at least 1 unsaturated
bond; and mixtures of various substitutions thereof. The
pentaerythriol esters also may contain compounds with mixtures of
different chain lengths for R. The pentaerythriol esters also may
contain compounds with mixtures of different chain lengths for R,
or mixtures of compounds where R.sup.1 comprises at least one
unsaturated bond with compounds where R.sup.1 is fully
saturated.
[0056] Compounds of Formulas (Ia), (Ib), and (Ic) can all be
bio-based derived. By "bio-based derived", it is meant that at
least 10% of the material can be produced from non-crude oil
sources, such as plants, other vegetation, and tallow. In one
embodiment, the compounds of formulas (Ia), (Ib), and (Ic) are from
about 10% to 100% bio-based. In one embodiment, the compounds of
formulas (Ia), (Ib), and (Ic) are from about 35% to 100% bio-based.
In one embodiment, the compounds of formulas (Ia), (Ib), and (Ic)
are from about 50% to 100% bio-based. In one embodiment, the
compounds of formulas (Ia), (Ib), and (Ic) are from about 75% to
100% bio-based. In one embodiment, the compounds of formulas (Ia),
(Ib), and (Ic) are 100% bio-based. At least one R, R.sup.3,
R.sup.4, R.sup.19 of each of Formulas (Ia), (Ib), and (Ic) is --H
to allow reactivity with isocyanate groups. The average OH value of
the compounds can range from just greater than 0 to about 230,
preferably about 10 to about 175, and most preferably from about 25
to about 140.
[0057] To make the polymer extender compounds of the present
invention, a compound of formula (Ia), (Ib), or (Ic), or mixtures
thereof, is reacted with an isocyanate group-containing isocyanate,
diisocyanate, polyisocyanate, or mixture thereof. The isocyanate
group-containing compound adds to the branched nature of the
polymer. The term "polyisocyanate" is defined as di- and
higher-functional isocyanates, and the term includes oligomers. Any
monoisocyanate or polyisocyanate having predominately two or more
isocyanate groups, or any isocyanate precursor of a polyisocyanate
having predominately two or more isocyanate groups, is suitable for
use in this invention. For example, hexamethylene diisocyanate
homopolymers are suitable for use herein and are commercially
available. It is recognized that minor amounts of diisocyanates can
remain in products having multiple isocyanate groups. An example of
this is a biuret containing residual small amounts of hexamethylene
diisocyanate.
[0058] Also suitable for use as the polyisocyanate reactant are
hydrocarbon diisocyanate-derived isocyanurate trimers. Preferred is
DESMODUR N-100 (a hexamethylene diisocyanate-based available from
Bayer Corporation, Pittsburgh, Pa.). Other triisocyanates useful
for the purposes of this invention are those obtained by reacting
three moles of toluene diisocyanate. The isocyanurate trimer of
toluene diisocyanate and that of
3-isocyanatomethyl-3,4,4-trimethylcyclohexyl isocyanate are other
examples of triisocyanates useful for the purposes of this
invention, as is methane-tris-(phenylisocyanate). Precursors of
polyisocyanate, such as diisocyanate, are also suitable for use in
the present invention as substrates for the polyisocyanates.
DESMODUR N-3300, DESMODUR N-3600, DESMODUR Z-4470, DESMODUR H,
DESMODUR N3790, and DESMODUR XP 2410, from Bayer Corporation,
Pittsburgh, Pa., and bis-(4-isocyanatocylohexyl)methane are also
suitable in the invention.
[0059] Preferred polyisocyanate reactants are the aliphatic and
aromatic polyisocyanates containing biuret structures, or
polydimethyl siloxane containing isocyanates. Such polyisocyanates
can also contain both aliphatic and aromatic substituents.
[0060] Particularly preferred as the (poly)isocyanate reactant for
all the embodiments of the invention herein are hexamethylene
diisocyanate homopolymers commercially available, for instance as
DESMODUR N-100, DESMODUR N-75 and DESMODUR N-3200 from Bayer
Corporation, Pittsburgh, Pa.;
3-isocyanatomethyl-3,4,4-trimethylcyclohexyl isocyanate available,
for instance as DESMODUR I (Bayer Corporation);
bis-(4-isocyanatocylohexyl)methane available, for instance as
DESMODUR W (Bayer Corporation) and diisocyanate trimers of formulas
(IIa), (IIb), (IIc) and (IId):
##STR00003##
[0061] The diisocyanate trimers (IIa-d) are available, for instance
as DESMODUR Z4470, DESMODUR IL, DESMODUR N-3300, and DESMODUR
XP2410, respectively, from Bayer Corporation.
[0062] In one embodiment, the reaction product of (a) an
isocyanate-containing compound with (b) an isocyanate-reactive
compound contains unreacted isocyanate groups which are further
reacted with (c) at least one second compound selected from water,
organic compounds of Formula (IIIa)
R.sup.5--X (IIIa),
organic compounds of Formula (IIIb)
R.sup.15--(OCH.sub.2CH(OR.sup.16)CH.sub.2).sub.z--OR.sup.17
(IIIb),
or mixtures thereof, wherein R.sup.5 is selected from a --C.sub.1
to C.sub.30 linear or branched alkyl optionally comprising at least
one unsaturated group, a hydroxy-functional C.sub.1 to C.sub.30
linear or branched alkyl, a hydroxy-functional linear or branched
C.sub.1 to C.sub.30 polyether, a hydroxy-functional linear or
branched polyester, a hydroxy-functional linear or branched
organosiloxane, a thiol-functional C.sub.1 to C.sub.30 linear or
branched alkyl, an amine-functional C.sub.1 to C.sub.30 linear or
branched alkyl,
##STR00004##
[0063] wherein R.sup.7, R.sup.8, and R.sup.9 are each
independently, --H, --C.sub.1 to C.sub.6 alkyl, or combinations
thereof; R.sup.10 is a divalent alkyl group of 1 to 20 carbons; X
is an isocyanate-reactive functional group such as --OH, --C(O)OH,
--SH, --NH(R.sup.12),
--O--(CH.sub.2CH.sub.2O).sub.s(CH(CH.sub.3)CH.sub.2O).sub.t--H or
--[C(O)]--O--(CH.sub.2CH.sub.2O).sub.s(CH(CH.sub.3)CH.sub.2O).sub.t--H;
R.sup.12 is --H or a monovalent C.sub.1 to C.sub.6 alkyl group;
R.sup.15, R.sup.16, and R.sup.17 are each independently a --H;
--R.sup.18; --C(O)R.sup.18 provided that at least one R.sup.15,
R.sup.16, or R.sup.17 is a --H; R.sup.18 is independently a linear
or branched alkyl group having 5 to 29 carbons optionally
comprising at least 1 unsaturated bond; z is 1 to 15; Y is --Cl; s
is an integer of 0 to 50; t is an integer of 0 to 50; s+t is
greater than 0. The term "branched", as used herein, means that the
functional chain can be branched at any point, for example as a
quarternary substituted carbon, and can contain any number of
branched substitutions.
[0064] In one embodiment, the second compound is present and reacts
with about 0.1 mol % to about 60 mol % of said isocyanate groups.
Preferably the concentration of compounds of isocyanate-reactive
compound (b) is greater than the concentration of second
compound(s) (c).
[0065] In one embodiment, the second compound (c) of the polymer
extender compound is water. Water may be used to crosslink
unreacted isocyanate groups by urea linkage. In a further
embodiment, the second compound (c) is of Formula (IIIa). The
compound of formula (IIIa) can be a hydrophilic water-solvatable
material comprising at least one hydroxy-terminated polyether of
formula (IIIa) wherein isocyanate-reactive group X is
--O--(CH.sub.2CH.sub.2O)(CH(CH.sub.3)CH.sub.2O).sub.t--H or
--[C(O)]--O--(CH.sub.2CH.sub.2O).sub.s(CH(CH.sub.3)CH.sub.2O).sub.t--H.
In this embodiment, --(CH.sub.2CH.sub.2O)-- represents oxyethylene
groups (EO) and --(CH(CH.sub.3)CH.sub.2O)-- represents oxypropylene
groups (PO). These polyethers can contain only EO groups, only PO
groups, or mixtures thereof. These polyethers can also be present
as a tri-block copolymer designated PEG-PPG-PEG (polyethylene
glycol-polypropylene glycol-polyethylene glycol). Preferably, the
polyethers are the commercially available methoxypolyethylene
glycols (MPEG's), or mixtures thereof. Also commercially available,
and suitable for the preparation of the compositions of the present
invention, are butoxypolyoxyalkylenes containing equal amounts by
weight of oxyethylene and oxypropylene groups (Union Carbide Corp.
50-HB Series UCON Fluids and Lubricants) and having an average
molecular weight greater than about 1000. The hydroxy-terminal
polyethers of Formula (IIIa) preferably have an average molecular
weight equal to or greater than about 200, and most preferably
between 350 and 2000.
[0066] In another embodiment, the second compound (c) is an organic
compound of Formula (IIIa), where isocyanate-reactive group X is
--OH, --C(O)OH, --SH, --NH(R.sup.12); and R.sup.5 is selected from
a --C.sub.1 to C.sub.30 linear or branched alkyl optionally
comprising at least one unsaturated group, a hydroxy-functional
C.sub.1 to C.sub.30 linear or branched alkyl, a hydroxy-functional
linear or branched C.sub.1 to C.sub.30 polyether, a
hydroxy-functional linear or branched polyester, a hydroxy- or
amine-functional linear or branched organosiloxane, a
thiol-functional C.sub.1 to C.sub.30 linear or branched alkyl, an
amine-functional C.sub.1 to C.sub.30 linear or branched alkyl.
[0067] Where isocyanate-reactive group X is --OH, examples of
Formula (IIIa) include but are not limited to alkyl alcohols such
as propanol, butanol, or fatty alcohols including stearyl alcohol
(R.sup.5 is a --C.sub.1 to C.sub.30 linear or branched alkyl
optionally comprising at least one unsaturated group); alkyl diols
or polyols such as ethanediol, propanediol, butanediol, or
hexanediol (R.sup.5 is a hydroxy-functional C.sub.1 to C.sub.30
linear or branched alkyl); alkylene glycol ethers such as
triethylene glycol, tetraethylene glycol, poly(ethylene glycol)
(PEG), poly(propylene glycol) (PPG), poly(tetrahydrofuran), or
glycol ethers having mixtures of PEG, PPG, or THF units (R.sup.5 is
a hydroxy-functional linear or branched C.sub.1 to C.sub.30
polyether); polyester polyols (R.sup.5 is a hydroxy-functional
linear or branched polyester); silicone prepolymer polyols (R.sup.5
is a hydroxy-functional linear or branched organosiloxane);
N,N-dimethylaminoethanol (R.sup.5 is an amine-functional C.sub.1 to
C.sub.30 linear or branched alkyl); choline chloride or betaine HCl
(R.sup.5 is Y.sup.- (R.sup.7)(R.sup.8)(R.sup.9)N.sup.+R.sup.10--);
butanone oxime (R.sup.5 is (R.sup.7)(R.sup.8)C.dbd.N--). The
polyether polyols can contain only EO groups, only PO groups, only
THF groups, or mixtures thereof. These polyethers can also be
present as a block copolymer, such as that designated by
PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene
glycol). Preferably, the polyether glycols have an average
molecular weight equal to or greater than about 200, and most
preferably between 350 and 2000.
[0068] Where isocyanate-reactive group X is --C(O)OH, examples of
Formula (IIIa) include but are not limited to fatty acids such as
caprylic acid, capric acid, lauric acid, mysteric acid, palmitic
acid, stearic acid, arachidic acid, behenic acid, lignoceric acid,
palmitoleic acid, lineolic acid, arachidonic acid, oleic acid, or
erucic acid (R.sup.5 is a --C.sub.1 to C.sub.30 linear or branched
alkyl optionally comprising at least one unsaturated group);
hydroxy-containing acids such as hydroxycaprylic acid,
hydroxycapric acid, hydroxylauric acid, hydroxymysteric acid,
hydroxypalmitic acid, hydroxystearic acid, hydroxyarachidic acid,
hydroxybehenic acid, hydroxylignoceric acid, hydroxypalmitoleic
acid, hydroxylineolic acid, hydroxyarachidonic acid, hydroxyoleic
acid, or hydroxyerucic acid (R.sup.5 is a hydroxy-functional
C.sub.1 to C.sub.30 linear or branched alkyl); and mercaptoalkanoic
acids such as mercaptopropionic acid (R.sup.5 is a thiol-functional
C.sub.1 to C.sub.30 linear or branched alkyl).
[0069] Where isocyanate-reactive group X is --SH, specific examples
of Formula (IIIa) include but are not limited to alkyl thiols such
as lauryl mercaptan or dodecyl mercaptan (R.sup.5 is a --C.sub.1 to
C.sub.30 linear or branched alkyl optionally comprising at least
one unsaturated group). Where isocyanate-reactive group X is
--NH(R.sup.12), specific examples of Formula (IIIa) include but are
not limited to alkyl amines such as diisopropylamine, propylamine,
hexylmine, or laurylamine (R.sup.5 is a --C.sub.1 to C.sub.30
linear or branched alkyl optionally comprising at least one
unsaturated group); alkanolamines such as ethanolamine or
propanolamine (R.sup.5 is a hydroxy-functional C.sub.1 to C.sub.30
linear or branched alkyl); silicone prepolymer polyamines (R.sup.5
is a amine-functional linear or branched organosiloxane); alkyl
diamines (R.sup.5 is an amine-functional C.sub.1 to C.sub.30 linear
or branched alkyl); and aminoalkanesulfonic acids such as
2-aminoethanesulfonic acid (R.sup.5 is
HO--S(O).sub.2R.sup.10--).
[0070] In a further embodiment, the second compound (c) of the
extender polymer is of formula (IIIb). These compounds are commonly
referred to as polyglycerols. These polyglycerols can be present
where R.sup.15, R.sup.16, and R.sup.17 are each independently a
--H; --R.sup.18; --C(O)R.sup.18 provided that at least one
R.sup.15, R.sup.16, or R.sup.17 is a --H; and wherein R.sup.18 is
independently a linear or branched alkyl group having 5 to 29
carbons optionally comprising at least 1 unsaturated bond. Specific
examples include but are not limited to triglycerol monostearate,
triglycerol distearate, hexaglycerol monostearate, hexaglycerol
distearate, decaglyceryl mono(carpylate/caprate), decaglyceryl
di(carpylate/caprate), decaglycerol, polyglycerol-3, and C18
diglyceride.
[0071] In one embodiment, the reaction product of (a) an
isocyanate-containing compound with (b) an isocyanate-reactive
compound contains unreacted isocyanate groups which are further
reacted with multiple second compounds (c) comprising both
compounds of formula (IIIa) or (IIIb) and water. Water is used to
cross-link unreacted isocyanates to creates urea linkages.
[0072] The polymer extender compounds of the present invention can
be made in one step. The polymer extender compounds of the present
invention comprising more than one organic compound of Formula
(Ia), (Ib), or (Ic) and/or on or more second compounds (c) can be
also made in one step. Preferably, if more than one organic
compounds of Formula (Ia), (Ib), or (Ic) and/or on or more second
compounds (c) are used, then the synthesis can be completed
sequentially. A sequential addition is especially useful when
employing compounds of Formula (Ia), (Ib), or (Ic) with high OH
numbers, or when using polyfunctional compounds (c). These steps
comprise reacting (a) at least one isocyanate group-containing
compound selected from isocyanate, diisocyanate, polyisocyanate, or
mixture thereof, and (b) at least one isocyanate-reactive compound
selected from formula (Ia), (Ib), or (Ic) wherein each R is
independently a --H; --R.sup.1; --C(O)R.sup.1;
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mR.sup.2; or
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mC(O)R.sup.1;
each n is independently 0 to 20; each m is independently 0 to 20;
m+n is greater than 0; each R.sup.1 is independently a linear or
branched alkyl group having 5 to 29 carbons optionally comprising
at least 1 unsaturated bond; each R.sup.2 is independently --H, or
a linear or branched alkyl group having 6 to 30 carbons optionally
comprising at least 1 unsaturated bond; or a mixtures thereof,
provided that when the compound is of Formula (Ia) then at least
one of R or R.sup.2 is --H; each R.sup.3 is independently a --H;
--R.sup.1; --C(O)R.sup.1;
--(CH.sub.2CH.sub.2O).sub.n'(CH(CH.sub.3)CH.sub.2O).sub.m'R.sup.2;
or
--(CH.sub.2CH.sub.2O).sub.n'(CH(CH.sub.3)CH.sub.2O).sub.m'C(O)R.sup.1;
each R.sup.4 is independently --H, a linear or branched alkyl group
having 6 to 30 carbons optionally comprising at least 1 unsaturated
bond, or combinations thereof;
--(CH.sub.2CH.sub.2O).sub.n'(CH(CH.sub.3)CH.sub.2O).sub.m'R.sup.2;
or
--(CH.sub.2CH.sub.2O).sub.n'(CH(CH.sub.3)CH.sub.2O).sub.m'C(O)R.sup.1;
each n' is independently 0 to 20; each m' is independently 0 to 20;
m'+n' is greater than 0; provided when the compound is Formula
(Ib), then at least one R.sup.2, R.sup.3 or R.sup.4 is a --H; and
each R.sup.19 is --H, --C(O)R.sup.1, or
--CH.sub.2C[CH.sub.2OR].sub.3, provided when the compound is
Formula (Ic), then at least one R.sup.19 or R is --H. When a second
compound (c) is used, molar concentrations of the at least one
compound selected from Formula (Ia), (Ib), or (Ic) are such that
there remains unreacted isocyanate groups to react with the one or
more second compound(s) (c).
[0073] The at least one isocyanate, diisocyanate, polyisocyanate,
or mixture thereof, and at least one isocyanate group-containing
compound selected from isocyanate, diisocyanate, polyisocyanate, or
mixture thereof, and (b) at least one isocyanate-reactive compound
selected from formula (Ia), (Ib), or (Ic), or mixture thereof, are
reacted. This reaction is typically conducted by charging a
reaction vessel with the isocyanate, diisocyanate, or
polyisocyanate, and at least one compound selected from formula
(Ia), (Ib), or (Ic), or mixture thereof, and optionally a second
compound (c). The order of reagent addition is not critical, but if
water is used, the water should be added after the isocyanates and
at least one compound selected from formula (Ia), (Ib), or (Ic), or
mixture thereof are reacted.
[0074] The specific weight of the reactants charged is based on
their equivalent weights and on the working capacity of the
reaction vessel, and is adjusted so that compound selected from
formula (Ia), (Ib), or (Ic) will be consumed in the first step. A
suitable dry organic solvent free of isocyanate-reactive groups is
typically used as a solvent. Ketones are the preferred solvents,
and methylisobutylketone (MIBK) is particularly preferred for
convenience and availability. The charge is agitated, and
temperature adjusted to about 40.degree. C. to 70.degree. C.
Typically, a catalyst such as iron(III) chloride in an organic
solvent is then added, typically in an amount of from about 0.01 to
about 1.0 weight % based on the dry weight of the composition, and
the temperature is raised to about 80.degree. C. to 100.degree. C.
A co-catalyst, such as sodium carbonate, may also be used. If water
is to be added, the initial reaction is conducted so that less than
100% of the isocyanate groups are reacted. In the second step after
holding for several hours, additional solvent, water, and
optionally a second compound (c) are added, and the mixture is
allowed to react for several more hours or until all of the
isocyanate has been reacted.
[0075] The extender compositions as described above are then
blended with any of a variety of known treating agents for fibrous
substrates, preferably in a weight ratio of extender:treating agent
from about 1:10 to about 10:1, more preferably a ratio of from
about 1:8 to 5:1, and most preferably in a ratio of from about 1:6
to 10:3. Examples include no iron, easy to iron, shrinkage control,
wrinkle free, permanent press, moisture control, softness,
strength, anti-slip, anti-static, anti-snag, anti-pill, stain
repellency, stain release, soil repellency, soil release, water
repellency, oil repellency, odor control, antimicrobial, sun
protection, and similar effects. Preferred treating agents are any
of those used for creating water or oil repellency on a fibrous
substrate. Such materials can be in the form of non-fluorinated
cationic acrylic polymers, non-fluorinated anionic acrylic
polymers, non-fluorinated nonionic acrylic polymers, partially
fluorinated urethanes, cationic partially fluorinated acrylic
polymers or copolymers, nonionic partially fluorinated acrylic
polymers or copolymers, partially fluorinated acrylamide polymers
or copolymers, silicones, or parafins.
[0076] Of particular interest are fluorinated polymers useful as
treating agents to provide repellency properties to the surface of
treated substrates. These include fluorochemical compounds or
polymers containing one or more fluoroaliphatic groups (designated
here as R.sub.f groups) which are fluorinated, stable, inert, and
non-polar, preferably saturated, monovalent, and both oleophobic
and hydrophobic. The R.sub.f groups contain at least 3 carbon
atoms, preferably 3 to 20 carbon atoms, more preferably 4 to 12
carbon atoms, and most preferably about 4 to about 6 carbon atoms.
The R.sub.f groups may contain straight or branched chain or cyclic
fluorinated alkylene groups or combinations thereof. The terminal
portion of the R.sub.f groups is preferably a perfluorinated
aliphatic group of the formula C.sub.nF.sub.2n+1 wherein n is from
about 3 to about 20. Examples of fluorinated polymer treating
agents are CAPSTONE and ZONYL available from E. I. du Pont de
Nemours and Company, Wilmington, Del.; ASAHI GARD from Asahi Glass
Company, Ltd., Tokyo, Japan; UNIDYNE from Daikin America, Inc.,
Orangeburg, N.Y.; SCOTCHGARD from 3M Company, St. Paul, Minn.; and
NANO TEX from Nanotex, Emeryville, Calif.
[0077] Examples of such fluorinated polymers preferably include
Rf-containing polyurethanes and poly(meth)acrylates. Especially
preferred are copolymers of fluorochemical (meth)acrylate monomers
with a co-polymerizable monovinyl compound or a conjugated diene.
The co-polymerizable monovinyl compounds include alkyl
(meth)acrylates, vinyl esters of aliphatic acids, styrene and alkyl
styrene, vinyl halides, vinylidene halides, alkyl esters, vinyl
alkyl ketones, and acrylamides. The conjugated dienes are
preferably 1,3-butadienes. Representative compounds within the
preceding classes include the methyl, propyl, butyl,
2-hydroxypropyl, 2-hydroxyethyl, isoamyl, 2-ethylhexyl, octyl,
decyl, lauryl, cetyl, and octadecyl acrylates and methacrylates;
vinyl acetate, vinyl propionate, vinyl caprylate, vinyl laurate,
vinyl stearate, styrene, alpha methyl styrene, p-methylstyene,
vinyl fluoride, vinyl chloride, vinyl bromide, vinylidene fluoride,
vinylidene chloride, allyl heptanoate, allyl acetate, allyl
caprylate, allyl caproate, vinyl methyl ketone, vinyl ethyl ketone,
1,3-butadiene, 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene,
isoprene, N-methylolacrylamide, N-methylolmethacrylamide, glycidyl
acrylate, glycidyl methacrylate, amine-terminated (meth)acrylates,
and polyoxy(meth)acrylates.
[0078] The blended composition comprising a treating agent and the
extender compositions of the present invention applied to the
fibrous substrate optionally further comprises a blocked isocyanate
to promote durability, added after copolymerization (i.e., as a
blended isocyanate). An example of a suitable blocked isocyanate is
PHOBOL XAN available from Huntsman Corp, Salt Lake City, Utah Other
commercially available blocked isocyanates are also suitable for
use herein. The desirability of adding a blocked isocyanate depends
on the particular application for the copolymer. For most of the
presently envisioned applications, it does not need to be present
to achieve satisfactory cross-linking between chains or bonding to
the fibers. When added as a blended isocyanate, amounts up to about
20% by weight are added.
[0079] The blended composition comprising a treating agent and the
extender composition of the present invention optionally further
comprises additional components such as additional treating agents
or finishes to achieve additional surface effects, or additives
commonly used with such agents or finishes. Such additional
components comprise compounds or compositions that provide surface
effects such as no iron, easy to iron, shrinkage control, wrinkle
free, permanent press, moisture control, softness, strength,
anti-slip, anti-static, anti-snag, anti-pill, stain repellency,
stain release, soil repellency, soil release, water repellency, oil
repellency, odor control, antimicrobial, sun protection, and
similar effects. One or more such treating agents or finishes can
be combined with the blended composition and applied to the fibrous
substrate. Other additives commonly used with such treating agents
or finishes may also be present such as surfactants, pH adjusters,
cross linkers, wetting agents, and other additives known by those
skilled in the art. Further, other extender compositions are
optionally included to obtain a combination of benefits.
[0080] For example, when synthetic fabrics are treated, a wetting
agent can be used, such as ALKANOL 6112 available from E. I. du
Pont de Nemours and Company, Wilmington, Del. As a further example,
when cotton or cotton-blended fabrics are treated, a
wrinkle-resistant resin can be used such as PERMAFRESH EFC
available from Emerald Carolina, LLC, Cahrlotte, N.C. As a further
example, when nonwoven fabrics are treated, a wax extender can be
employed such as FREEPEL 1225WR, available from Omnova Solutions
Chester, S.C. An antistat such as ZELEC KC, available from Stepan,
Northfield, Ill., or a wetting agent, such as hexanol, also are
suitable. The dispersions are generally applied to fibrous
substrates by spraying, dipping, padding, or other well-known
methods. After excess liquid has been removed, for example by
squeeze rolls, the treated fibrous substrate is dried and then
cured by heating, for example, to from about 100.degree. C. to
about 190.degree. C., for at least 30 seconds, typically from about
60 to about 240 seconds. Such curing enhances oil-, water- and soil
repellency and durability of the repellency. While these curing
conditions are typical, some commercial apparatus may operate
outside these ranges because of its specific design features.
[0081] The present invention further comprises substrates treated
with the above-described composition comprising i) a treating agent
which provides a surface effect and ii) the extender compounds as
described above. The composition also can contain optional agents
to provide additional surface effects as described above, optional
additives commonly used in treating substrates as described above,
optional blocked isocyanate as described above, and optional
additional distinct extender compositions. As previously noted such
substrates include paper, nonwovens, leather, fibers, textiles,
fabrics, fabric blends, or combinations thereof. "Fabrics" includes
natural or synthetic fabrics composed of fibers of cotton, rayon,
silk, wool, polyester, polypropylene, polyolefins, nylon, and
aramids such as "NOMEX" and "KEVLAR." By "fabric blends" is meant
fabric made of two or more types of fibers. Typically these blends
are a combination of at least one natural fiber and at least one
synthetic fiber, but also can be a blend of two or more natural
fibers or of two or more synthetic fibers. Preferably, the
substrate has been treated with a composition comprising an
extender composition of the present invention and a fluorinated
polymer such as a polyurethane or poly(meth)acrylate.
[0082] Specifically, the method and treated substrates of the
present invention are useful to enhance surface properties,
especially durability of oil-, water- and soil-repellency, of the
above-described substrates while reducing the amount of fluorinated
polymer employed. The repellency property is more durable than
applications of fluorinated polymer treating agents with other
extenders, and is effective for various fibrous substrates. The
repellency property is effective with a variety of other surface
effects. The treated fibrous substrates of the present invention
are useful in a variety of applications such as for textiles,
clothing, uniforms, protective garments, furnishings, and the like.
The extender composition of the present invention are advantageous
in that when blended with fluorinated polymer treating agents, they
give highly durable, low yellowing repellent finishes over a wide
range of fibrous substrates while using a reduced level of the
fluorinated polymer.
Test Methods
[0083] All solvents and reagents, unless otherwise indicated, were
purchased from Sigma-Aldrich, St. Louis, Mo., and used directly as
supplied. Sorbitan tristearate was obtained from Croda, East
Yorkshire, England and DuPont Nutrition & Health, Copenhagen,
Denmark. DESMODUR N-100 was obtained from Bayer Corporation,
Pittsburgh, Pa. ARMEEN DM-18D was obtained from Akzo-Nobel,
Bridgewater, N.J. PHOBOL XAN was obtained from Huntsman Corp, Salt
Lake City, Utah
[0084] The cationic dispersed non-fluorinated acrylic copolymer
(repellent product), cationic self-dispersed fluorinated
(meth)acrylate/amine-terminated (meth)acrylate/reactive
(meth)acrylate copolymer (water repellent and stain release agent),
and cationic dispersed partially fluorinated
(meth)acrylate/vinylidene chloride/alkyl (meth)acrylate copolymer
(water repellent agent) are commercially available from DuPont de
Nemours, Wilmington, Del.
[0085] The following tests were employed in evaluating the examples
herein.
Test Method 1--Fabric Treatment
[0086] The fabrics treated in this study were 100% by weight khaki
cotton twill available from SDL Atlas Textile Testing Solutions,
Rock Hill, S.C. 29732 and 100% by weight red polyester fabric
available from L. Michael OY, Finland. The fabric was treated with
the aqueous dispersions various emulsion polymer using a
conventional pad bath (dipping) process. The prepared concentrated
dispersion of the polymer emulsions were diluted with deionized
water to achieve a pad bath having 60 g/L of the final emulsion in
the bath. For the treatment of the cotton fabric, a wetting agent,
INVADINE PBN and a catalyzed cross-linking agent, KNITTEX 7636 (all
available from Huntsman, Salt Lake City, Utah) were also included
in the bath at 5 g/L and 30 g/L respectively. The fabric was padded
in the bath, and the excess liquid was removed by squeeze rollers.
The wet pickup was around 95% on the cotton substrate. The "wet
pick up" is the weight of the bath solution of the emulsion polymer
and additives applied to the fabric, based on the dry weight of the
fabric. The fabric was cured at approximately 165.degree. C. for 3
minutes and allowed to "rest" after treatment and cure for at least
2 hours.
[0087] For the treatment of the polyester fabric, a wetting agent,
INVADINE.RTM. PBN (available from Huntsman, Charlotte, N.C., USA)
and 20% acetic acid were also included in the bath at 5 g/L and 1
g/L respectively. The fabric was padded in the bath, and the excess
liquid removed by squeeze rollers. The wet pickup was around 55% on
the polyester substrate. The "wet pick up" is the weight of the
bath solution of the emulsion polymer and additives applied to the
fabric, based on the dry weight of the fabric. The fabric was cured
at approximately 160.degree. C. for 2 minutes and allowed to "rest"
after treatment and cure for about 15 to about 18 hours.
Test Method 2--Water Drop Repellency
[0088] The water repellency of a treated textile substrate was
measured according to AATCC standard Test Method No. 193 and the
method outlined in the Teflon.RTM. Global Specifications and
Quality Control Tests booklet.
Test Method 3--Water Spray Repellency
[0089] Water repellency was further tested by utilizing the spray
test method which is a measure of dynamic water repellency. The
treated fabric samples were tested for water repellency according
to AATCC standard Test Method No. 22 and the method outlined in the
Teflon.RTM. Global Specifications and Quality Control Tests
booklet.
Test Method 4--Oil Repellency
[0090] The treated fabric samples were tested for oil repellency by
a modification of AATCC standard Test Method No. 118, and the
method outlined in the Teflon.RTM. Global Specifications and
Quality Control Tests booklet.
Test Method 4--Bundesmann Absorbency
[0091] The treated fabric samples were tested for dynamic water
absorbency after 30 homewashes following ISO 9865 standard Test
Method.
Test Method 5--Abrasion Test Method
[0092] The treated fabric samples were tested for abrasion using
modified AATCC standard Test Method No. 8, and the method outlined
in the Teflon.RTM. Global Specifications and Quality Control Tests
booklet.
Test Method 6--Wash Durability
[0093] The fabric samples were laundered according to International
Standard specified domestic washing procedure for textile testing.
Fabric samples were loaded into a horizontal drum, front-loading
type (Type A, WASCATOR FOM 71MP-Lab) of automatic washing machine
with a ballast load to give a total dry load of 4 lb. A commercial
detergent was added (AATCC 1993 standard Reference Detergent WOB)
and the washer program ISO 7A was used. After washing was complete,
the entire load was placed into a KENMORE automatic dryer and dried
on high for 45-50 min.
Examples
Formulation Compositions
[0094] Formulations were made using the ingredients listed in
Tables 1, 4, 7, and 10. Ingredients were added to a glass bottle
and stirred for 5 minutes to ensure sufficient mixing.
Urethane Based Extender 1
[0095] In a 4-neck round bottom flask equipped with an overhead
stirrer, thermocouple, dean-stark/condenser was added sorbitan
tristearate (116.0 g; Hydroxy Number=77.2 mgKOH/g) and
4-methyl-2-pentanone (MIBK, 150 g). The solution was heated to
50.degree. C. and DESMODUR N-100 (30 g) was added followed by a
catalyst and the solution was heated to 80.degree. C. over one
hour.
Urethane Based Extender 2
[0096] In a 4-neck round bottom flask equipped with an overhead
stirrer, thermocouple, dean-stark/condenser was added sorbitan
tristearate (116.0 g; Hydroxy Number=77.2 mgKOH/g) and
4-methyl-2-pentanone (MIBK, 150 g). The solution was refluxed for 1
hour to remove any residual moisture. After the hour, the solution
was cooled to 50.degree. C. and DESMODUR N-100 (30 g) was added
followed by a catalyst and the solution was heated to 80.degree. C.
over one hour.
Urethane Based Extender 3
[0097] In a 4-neck round bottom flask equipped with an overhead
stirrer, thermocouple, dean-stark/condenser was added sorbitan
tristearate (125.4 g; Hydroxy Number=69.5 mgKOH/g) and
4-methyl-2-pentanone (MIBK, 150 g). The solution was refluxed for 1
hour to remove any residual moisture. After the hour, the solution
was cooled to 50.degree. C. and DESMODUR N-100 (30 g) was added
followed by a catalyst and the solution was heated to 80.degree. C.
over one hour.
Urethane Based Extender 4
[0098] In a 4-neck round bottom flask equipped with an overhead
stirrer, thermocouple, dean-stark/condenser was added sorbitan
tristearate (127.5 g; Hydroxy Number=69.0 mgKOH/g) and
4-methyl-2-pentanone (MIBK, 150 g). The solution was refluxed for 1
hour to remove any residual moisture. After the hour, the solution
was cooled to 50.degree. C. and DESMODUR N-100 (30 g) was added
followed by a catalyst and the solution was heated to 80.degree. C.
over one hour.
Urethane Based Extender 5
[0099] In a 4-neck round bottom flask equipped with an overhead
stirrer, thermocouple, dean-stark/condenser was added sorbitan
tristearate (120.5 g; Hydroxy Number=70.5 mgKOH/g) and
4-methyl-2-pentanone (MIBK, 150 g). The solution was refluxed for 1
hour to remove any residual moisture. After the hour, the solution
was cooled to 50.degree. C. and DESMODUR N-100 (30 g) was added
followed by a catalyst and the solution was heated to 80.degree. C.
over one hour.
Urethane Based Extender 6
[0100] In a 4-neck round bottom flask equipped with an overhead
stirrer, thermocouple, dean-stark/condenser was added sorbitan
tristearate (126.4 g of mixed sorbitan stearate esters; Hydroxy
Number=69.2 mgKOH/g) and 4-methyl-2-pentanone (MIBK, 150 g). The
solution was refluxed for 1 hour to remove any residual moisture.
After the hour, the solution was cooled to 50.degree. C. and
DESMODUR N-100 (30 g) was added followed by a catalyst and the
solution was heated to 80.degree. C. over one hour.
Urethane Based Extender Dispersion
[0101] Aqueous dispersions of Urethane Based Extenders 1-6,
described above, were prepared. Water (300 g), ARMEEN DM-18D (5.6
g), TERGITOL TMN-10 (2.8 g), and acetic acid (3.4 g) was added to a
beaker and stirred to from a surfactant solution. The solution as
heated to 60.degree. C. The sorbitan urethane/MIBK solution,
prepared as described above (Urethane Based Extenders 1-6), was
cooled to 60.degree. C. and the surfactant solution was added
slowly to produce a milky emulsion. Following homogenization at
6000 psi, the emulsion was distilled under reduced pressure to
remove the solvent, yielding non-flammable urethane dispersion at
25% solids.
Examples 1 to 5
[0102] Examples 1 to 5 were prepared by adding a dispersion of
Urethane Based Extender 1 to a cationic dispersed partially
fluorinated (meth)acrylate/vinylidene chloride/alkyl (meth)acrylate
copolymer (water repellent agent) at various ratios as described in
Table 1. A blocked isocyanate was also added to the dispersion. The
examples were applied to khaki cotton and polyester substrates and
tested according to the test methods as described above. Results
can be found in Tables 2 and 3.
Comparative Example A
[0103] Comparative Example A was prepared by adding a dispersion of
Urethane Based Extender 1 to a blocked isocyanate according to the
amounts in Table 1. The examples were applied to khaki cotton and
polyester substrates and tested according to the test methods as
described above. Results can be found in Tables 2 and 3.
Comparative Example B
[0104] Comparative Example B was prepared by using the fluorinated
copolymer used in Examples 1 to 5 but excluded the urethane based
extender and diluted to the same fluorinated content as Example 1.
The comparative example A was applied to khaki cotton and polyester
substrates and tested according to the test methods as described
above. Results can be found in Tables 2 and 3.
Comparative Example C
[0105] Comparative Example C was repeat of Example 1 except that a
commercially available cationic dispersed non-fluorinated acrylic
copolymer (repellent product) was used in place of Urethane Based
Extender 1. The comparative example C was applied to khaki cotton
and polyester substrates and tested according to the test methods
as described above. Results can be found in Tables 2 and 3.
TABLE-US-00001 TABLE 1 Extender Compositions of Examples 1 to 5 and
Comparative Examples A to C. Wt. % Component Example Fluorinated
Urethane Based PHOBOL % No. Copolymer Extender 1 XAN Water F 1 50
30.0 5.0 15.0 5.75 2 40 40.0 5.0 15.0 4.60 3 30 50.0 5.0 15.0 3.45
4 20 60.0 5.0 15.0 2.30 5 10 70.0 5.0 15.0 1.15 Comparative 0 80.0
5.0 15.0 0.0 Example A Comparative 50 0 0.sup.a 50 5.75 Example B
Comparative 50 30.0 (non- 5.0 15.0 5.75 Example C fluorinated
polyacrylate extender) .sup.a10 g/L PHOBOL XAN added to pad bath
for Comparative Example B.
TABLE-US-00002 TABLE 2 Performance results of Examples 1 to 5 and
Comparative Examples A to C on khaki bottom-weight cotton, 60 g/L
loading Ex 1 Ex 2 Ex 3 Ex 4 Ex 5 Comp. Ex. A Comp. Ex. B Comp. Ex.
C Water Drop Initial 6 6 6 6 6 4 6 6 30 HW 6 6 6 6 6 4 6 6 10x
abrasion 6 6 6 6 6 4 6 6 20x abrasion 6 6 6 6 5 4 6 6 30x abrasion
6 6 6 6 5 4 6 6 Oil Rating Initial 5.5 5.5 5.5 5.5 5 0 5.5 5.5 30
HW 5.5 5.5 5.5 5.5 5 0 5.5 5.5 10x abrasion 4 3 2 2 1 0 5.5 5.5 20x
abrasion 3 2 2 1 0 0 5 4 30x abrasion 2 2 1 1 0 0 3 3 Spray Rating
Initial 100 100 100 100 100 100 100 100 30 HW 85 85 85 85 85 80 90
80 Bundesmann after 30 HW % Absorbance 18.82 26.93 27.43 29.27
32.63 34.44 32.21 48.72
TABLE-US-00003 TABLE 3 Performance results Examples 1 to 5 and
Comparative Examples A to C on red polyester, 60 g/L loading Ex 1
Ex 2 Ex 3 Ex 4 Ex 5 Comp. Ex. A Comp. Ex. B Comp. Ex. C Water Drop
Initial 6 6 6 6 6 4 6 6 30 HW 6 6 6 6 6 4 6 6 10x abrasion 6 6 5 5
5 4 6 6 20x abrasion 6 6 5 5 4 4 6 6 30x abrasion 5 5 5 4 4 3 6 6
Oil Rating Initial 5 5 5 5 3 0 5 5 30 HW 5 5 5 5 3 0 5 5 10x
abrasion 3 3 2 1 1 0 3 5 20x abrasion 3 2 1 1 1 0 3 4 30x abrasion
2 2 1 0 0 0 3 4 Spray Rating Initial 100 100 100 100 100 100 100
100 30 HW 100 100 100 90 90 100 100 100 Bundesmann after 30 HW %
Absorb. 2.72 4.18 4.05 10.76 11.83 7.48 7.88 12.06
Examples 6 to 10
[0106] Examples 6 to 10 were prepared by adding a dispersion of
Urethane Based Extender 1 to a cationic self-dispersed fluorinated
(meth)acrylate/amine-terminated (meth)acrylate/reactive
(meth)acrylate copolymer (water repellent and stain release agent)
at various ratios as described in Table 4. A blocked isocyanate was
also added to the dispersion. The examples were applied to khaki
cotton and polyester substrates and tested according to the test
methods as described above. Results can be found in Tables 5 and
6.
Comparative Examples D to F
[0107] Comparative Examples D to F were prepared by adding a
dispersion of Urethane Based Extender 1, a cationic self-dispersed
fluorinated (meth)acrylatelamine-terminated (meth)acrylate/reactive
(meth)acrylate copolymer (water repellent and stain release agent),
and a blocked isocyanate according to the amounts in Table 4. The
examples were applied to khaki cotton and polyester substrates and
tested according to the test methods as described above. Results
can be found in Tables 5 and 6.
TABLE-US-00004 TABLE 4 Extender Compositions for Examples 6 to 10
and Comparative Examples D to F. Wt. % Component Example
Fluorinated Urethane Based PHOBOL % No. Copolymer Extender 1 XAN
Water F 6 50 30 5.0 15.0 3.4 7 40 40 5.0 15.0 2.7 8 30 50 5.0 15.0
2.0 9 20 60 5.0 15.0 1.4 10 10 70 5.0 15.0 0.7 Comparative 0 80 5.0
15.0 0.0 Example D Comparative 80 0 5.0 15.0 6.8 Example E
Comparative 50 0 0.sup.a 50 3.4 Example F .sup.a10 g/L PHOBOL XAN
added to pad bath for Comparative Example F.
TABLE-US-00005 TABLE 5 Performance results for Examples 6 to 10 and
Comparative Examples D to F on khaki bottom-weight cotton, 60 g/L
loading Ex 6 Ex 7 Ex 8 Ex 9 Ex 10 Comp. Ex. D Comp. Ex. E Comp. Ex.
F Water Drop Initial 3 3 3 3 3 3 3 3 30 HW 3 3 3 3 3 3 3 3 10x
abrasion 3 3 3 3 3 3 3 3 20x abrasion 3 3 3 3 3 3 3 3 30x abrasion
3 3 3 3 3 3 3 3 Oil Rating Initial 5 4 4 3 1 0 6 5 30 HW 3 2 2 1 0
0 5 4 10x abrasion 2 1 1 1 0 0 5 3 20x abrasion 2 1 1 1 0 0 5 3 30x
abrasion 2 1 1 1 0 0 5 3 Spray Rating Initial 70 80 70 70 75 100 80
80 30 HW 70 80 80 75 80 100 80 70 Corn Oil Stain Release Ratings
Initial 2 2 2 1 1 1 3 2 30 HW 1 1 1 1 1 1 5 3.5 Mineral Oil Stain
Release Ratings Initial 2 2 1 1 1 1 3.5 3 30 HW 1 1 1 1 1 1 4.5
4
TABLE-US-00006 TABLE 6 Performance results for Examples 6 to 10 and
Comparative Examples D to F on red polyester, 60 g/L loading Ex 6
Ex 7 Ex 8 Ex 9 Ex 10 Comp. Ex. D Comp. Ex. E Comp. Ex. F Water Drop
Initial 2 2 2 2 2 3 3 3 30 HW 3 3 3 3 3 3 3 3 10x abrasion 3 3 3 3
0 0 3 3 20x abrasion 3 3 3 3 0 0 3 3 30x abrasion 3 3 3 3 0 0 3 3
Oil Rating Initial 5 5 5 4 2 0 5 5 30 HW 4 3 3 2 0 0 5 4 10x
abrasion 1 1 1 0 0 0 4 3 20x abrasion 1 1 0 0 0 0 3 2 30x abrasion
1 1 0 0 0 0 3 2 Spray Rating Initial 50 50 30 30 30 100 70 60 30 HW
70 70 60 60 80 100 75 75 Corn Oil Stain Release Ratings Initial 3.5
3 2 2 1 1 5 3 30 HW 2 1 2 1 1 1 3 2 Mineral Oil Stain Release
Ratings Initial 2 1 2 1 1 1 1 1 30 HW 1 1 2 1 1 1 1 1
Examples 11 to 15
[0108] Examples 11 to 15 were prepared by adding a dispersion of
Urethane Based Extender 2 to a cationic self-dispersed fluorinated
(meth)acrylate/amine-terminated (meth)acrylate/reactive
(meth)acrylate copolymer (water repellent and stain release agent)
at various ratios as described in Table 7. A blocked isocyanate was
also added to the dispersion. The examples were applied to khaki
cotton and polyester substrates and tested according to the test
methods as described above. Results can be found in Tables 8 and
9.
Comparative Examples G to I
[0109] Comparative Examples G to I were prepared by adding a
dispersion of Urethane Based Extender 2, a cationic self-dispersed
fluorinated (meth)acrylate/amine-terminated (meth)acrylate/reactive
(meth)acrylate copolymer (water repellent and stain release agent),
and a blocked isocyanate according to the amounts in Table 7. The
examples were applied to khaki cotton and polyester substrates and
tested according to the test methods as described above. Results
can be found in Tables 8 and 9.
TABLE-US-00007 TABLE 7 Extender Compositions for Examples 11 to 15
and Comparative Examples G to I. Wt. % Component Example
Fluorinated Urethane Based PHOBOL % No. Copolymer Extender 2 XAN
Water F 11 50 30 5.0 15.0 5.3 12 40 40 5.0 15.0 4.2 13 30 50 5.0
15.0 3.2 14 20 60 5.0 15.0 2.1 15 10 70 5.0 15.0 1.1 Comparative 0
80 5.0 15.0 0.0 Example G Comparative 100 0 0.sup.a 0 10.5 Example
H Comparative 50 0 0.sup.a 50 5.3 Example I .sup.a10 g/L PHOBOL XAN
added to pad bath for Comparative Examples H and I.
TABLE-US-00008 TABLE 8 Performance results for Examples 11 to 15
and Comparative Examples G to I on khaki bottom-weight cotton, 60
g/L loading Ex 11 Ex 12 Ex 13 Ex 14 Ex 15 Comp. Ex. G Comp. Ex. H
Comp. Ex. I Water Drop Initial 6 5 5 5 5 4 6 6 30 HW 5 5 5 5 5 4 5
5 10x abrasion 5 4 4 4 4 4 6 6 20x abrasion 5 4 4 4 4 4 6 6 30x
abrasion 5 4 4 4 4 4 6 6 Oil Rating Initial 4 4 4 3 3 0 5 5 30 HW 2
2 2 1 1 0 3 2 10x abrasion 2 1 1 1 1 0 3 3 20x abrasion 1 1 1 1 1 0
3 3 30x abrasion 1 1 1 1 1 0 3 3 Spray Rating Initial 80 80 80 75
75 100 75 80 30 HW 85 90 90 80 75 100 50 90 Bundesmann after 30 HW
% Absortaance 50.75 51.39 45.36 44.36 41.24 30.47 71.86 52.74
TABLE-US-00009 TABLE 9 Performance results for Examples 11 to 15
and Comparative Examples G to I on red polyester, 60 g/L loading Ex
11 Ex 12 Ex 13 Ex 14 Ex 15 Comp. Ex. G Comp. Ex. H Comp. Ex. I
Water Drop Initial 5 5 5 4 4 4 5 5 30 HW 3 3 3 3 3 3 5 3 10x
abrasion 4 4 4 4 4 4 4 4 20x abrasion 4 4 4 4 4 4 4 4 30x abrasion
4 4 4 4 4 4 4 4 Oil Rating Initial 2 3 2 2 1 0 2 2 30 HW 0 0 0 0 0
0 1 0 10x abrasion 0 0 0 0 0 0 1 0 20x abrasion 0 0 0 0 0 0 0 0 30x
abrasion 0 0 0 0 0 0 0 0 Spray Rating Initial 75 80 80 80 80 100 80
75 30 HW 80 75 80 80 80 100 80 70 Bundesmann after 30 HW %
Absorbance 22.2 23.55 19.74 15.91 17.8 3.1 20.03 23.3
Examples 16 to 19
[0110] Examples 16 to 19 were prepared by adding a dispersion of
urethane based extender to a cationic dispersed partially
fluorinated (meth)acrylate/vinylidene chloride/alkyl (meth)acrylate
copolymer (water repellent agent) at various ratios as described in
Table 10. A blocked isocyanate was also added to the dispersion.
The examples were applied to khaki cotton and polyester substrates
and tested according to the test methods as described above.
Results can be found in Tables 11 and 12.
Comparative Examples J to N
[0111] Comparative Examples J to N were prepared by adding a
dispersion of urethane based extender, a cationic dispersed
partially fluorinated (meth)acrylate/vinylidene chloride/alkyl
(meth)acrylate copolymer (water repellent agent) and a blocked
isocyanate according to the amounts in Table 10. The examples were
applied to khaki cotton and polyester substrates and tested
according to the test methods as described above. Results can be
found in Tables 11 and 12.
TABLE-US-00010 TABLE 10 Extender Compositions for Examples 16 to 19
and Comparative Examples J to N. Wt. % Component Urethane Urethane
Urethane Urethane Example Fluorinated Based Based Based Based No.
Copolymer Extender 3 Extender 4 Extender 5 Extender 6 PHOBOL XAN
Water % F 16 50 30 0 0 0 5.0 15.0 5.3 Comp. Ex. J 0 80 0 0 0 5.0
15.0 0 17 50 0 30 0 0 5.0 15.0 5.3 Comp. Ex. K 0 0 80 0 0 5.0 15.0
0 18 50 0 0 30 0 5.0 15.0 5.3 Comp. Ex. L 0 0 0 80 0 5.0 15.0 0 19
50 0 0 0 30 5.0 15.0 5.3 Comp. Ex. M 0 0 0 0 80 5.0 15.0 0 Comp.
Ex. N 50 0 0 0 0 0.sup.a 50 5.3 .sup.a10 g/L PHOBOL XAN added to
pad bath for Comparative Example N.
TABLE-US-00011 TABLE 11 Performance results for Examples 16 to 19
and Comparative Examples J to N on khaki bottom-weight cotton, 60
g/L loading Ex 16 Comp. Ex. J Ex 17 Comp. Ex. K Ex 18 Comp. Ex. L
Ex. 19 Comp. Ex. M Comp. Ex. N Water Drop Initial 6 3 6 3 6 3 6 3 6
30 HW 6 3 6 3 6 3 6 3 6 Oil Rating Initial 6 0 6 0 6 0 6 0 6 30 HW
6 0 6 0 6 0 6 0 6 Bundesmann after 30 HW % Absorbance Initial 15.13
26.42 11.67 33.56 19.96 26.44 12.94 27.59 15.80 30 HW 17.65 39.45
22.36 39.86 25.10 43.46 23.45 49.18 22.16
TABLE-US-00012 TABLE 12 Performance results for Examples 16 to 19
and Comparative Examples J to N on on red polyester, 60 g/L loading
Ex 16 Comp. Ex. J Ex 17 Comp. Ex. K Ex 18 Comp. Ex. L Ex. 19 Comp.
Ex. M Comp. Ex. N Water Drop Initial 6 3 5 3 6 3 6 3 6 30 HW 6 3 6
3 6 3 6 3 5 Oil Rating Initial 4 0 4 0 4 0 4 0 4 30 HW 4 0 4 0 4 0
4 0 3 Bundesmann after 30 HW % Absorbance Initial 0.00 1.04 0.00
5.58 0.00 6.23 0.00 7.92 1.09 30 HW 0.01 1.67 0.00 4.41 0.00 5.46
5.56 1.72 3.98
* * * * *